Azo dyes from a 5-aminopyrazole bearing 1 to 2 sulfated hydroxyalkoxycarbonyl or N-(hydroxyalkyl) carbamoyl groups on its ring

ABSTRACT

This invention relates to azo dyes in which the diazotized amino component bears 1 or 2 sulfated hydroxyalkoxycarbonyl or N-(hydroxyalkyl)carbamoyl groups on its ring. These dyes have excellent dyeing properties on polyamide fibers and also impart color to cellulose acetate fibers and wool. 
     The dyes correspond to the formula: ##STR1## wherein when n is 1, R 1  is selected from hydrogen, alkyl, aryl, alkylthio, carbamoyl, alkylcarbamoyl, acyl, cyanoalkyl, and halogen; R is selected from hydrogen, alkyl, aryl, acyl, alkylsulfonyl, arylsulfonyl alkylsulfamoyl, arylsulfamoyl, alkyl substituted with alkoxy, cyano, or halogen, and aryl substituted with alkoxy, halogen, or cyano; X&#39; is O, NH, N(alkyl)--or N(aryl)--; Z is selected from straight- or branched-chain alkylene which may be substituted, for example, with phenyl, halogen, OSO 3  M, alkoxy, aryloxy and the like; M is H, Na, K or NH 4  ; n is 1 or 2; and the coupler C is selected from a variety of couplers including anilines, tetrahydroquinolines, phenols and the like.

This invention concerns novel dyes in which the diazo moieties contain sulfate groups. These dyes are substantially water soluble and are particularly useful for dyeing polyamide, wool and the like, and exhibit excellent properties including fastness to light and dyeability.

The dyes of this invention correspond to the general formula: ##STR2## wherein D is a pyrazol-5-yl radical which may be substituted further as defined below; C is the coupler portion of the molecule; X' is O, NH N(alkyl)--, or N(aryl)--; Z is selected from straight- or branched-chain alkylene, which may be substituted, for example, with phenyl, halogen, OSO₃ M, alkoxy or aryloxy groups, --CH₂ (CH₂)_(m) V--CH₂ (CH₂)_(p) --, where m is 1, 2 or 3, p is , 1, 2 or 3, and V is O, S, SO₂, --SO₂ NH--, --SO₂ N(alkyl)--, --SO₂ N(aryl), --N(SO₂ aryl)--, --NH, --NHCO--, --NHCONH, --N(SO₂ alkyl), or --CON(alkyl); M is H, Na, K or NH₄ ; and n is 1 or 2.

More particularly, the dyes correspond to the formula above wherein D represents the radical ##STR3## wherein the pyrazol-5-yl ring, in addition to the ##STR4## group where n is 1, may have a substituent R¹ selected from hydrogen, alkyl, aryl, alkylthio, carbamoyl, alkylcarbamoyl, acyl, cyanoalkyl, and halogen; R is selected from hydrogen, alkyl, aryl, acyl, alkylsulfonyl, arylsulfonyl, alkylsulfamoyl, arylsulfamoyl, alkyl substituted with alkoxy, cyano, or halogen, and aryl substituted with alkoxy, halogen, or cyano; and the coupler C is selected from ##STR5## wherein R² and R¹⁴ each represents up to three groups selected from hydrogen, fluorine, chlorine, bromine, alkyl, cycloalkyl, alkoxy, phenoxy, alkylthio, arylthio, and radicals having the formula --NH--X--R³ in which X is --CO--, --COO--, or --SO₂ -- and R³ is selected from alkyl and alkyl substituted with halogen hydroxy, phenoxy, aryl, cyano, cycloalkyl, alkylsulfonyl, alkylthio, alkanoyloxy, and alkoxy, and when X is --CO--, R³ also is selected from hydrogen, amino, alkylamino, alkylcarbamoyl, dialkylamino, arylamino, aryl, and furyl;

R⁴ and R⁵ are each selected from hydrogen, alkyl, aryl, cycloalkyl, and R⁴ and R⁵ together represent a single, combined group --CH₂ CH₂ CH₂ CH₂ CH₂ --, --CH₂ CH₂ OCH₂ CH₂ --, --CH₂ CH₂ --S--CH₂ CH₂ --, and --CH₂ CH₂ --SO₂ --CH₂ CH₂ --;

R⁸ is one or two groups each selected from hydrogen, alkyl and alkyl substituted with --CN, alkoxy, alkoxycarbonyl, alkoxycarbonyloxy, phenyl, cyclohexoxy, --OH, --Cl and Br;

R⁹, R¹⁰ and R¹¹ are each selected from hydrogen, alkyl, phenyl, or phenyl substituted with 1-3 groups selected from Cl, Br, alkyl or alkoxy, alkylthio, benzylthio, cyclohexylthio, phenylthio and substituted phenylthio;

Q and Q' are each selected from --CO--, --SO₂ --, or --CN; R¹² and R¹³ are each selected from hydrogen, alkyl, hydroxyalkyl, alkoxy, alkoxycarbonylamino, trifluoromethyl, phenyl or phenyl substituted with 1-3 groups selected from Cl, Br, alkyl or alkoxy, alkoxycarbonylalkyl, cyanoalkyl, amino, haloalkyl, alkylamino, alkylthio, benzylthio, cyclohexylthio, phenylthio and substituted phenylthio; R¹² and R¹³ may combine to form an alkylene bridge of 2 or 3 carbons, or to form an arylene or cycloalkylene radical of 5-6 carbons connecting Q and Q'; R¹⁶ and R¹⁷ are selected from hydrogen, cycloalkyl, aryl, alkyl, and alkyl substituted with alkoxy, hydroxy, alkoxyalkoxy, hydroxyalkoxy, carbamoyl, sulfamoyl, acylamido or alkenylsulfonyl, and aryl substituted with hydroxyalkyl; e is 1 or 2; and t and t' are each 1 or zero. It is noted that when t or t' is zero, the corresponding Q or Q' group is --CN;

Each of the aliphatic portions of the above alkyl, cycloaliphatic, alkoxy, alkanoyl and the like groups, as well as the aryl and aryloxy groups, may be substituted further with up to three of the following: hydroxy; halogen; cyano; succinimido; glutarimido; phthalimido; 2-pyrrolidono; cyclohexyl; phenyl or phenyl substituted with alkyl, alkoxy, halogen, alkanoylamino, cyano or alkoxycarbonyl; alkanoylamino; sulfamoyl; alkylsulfamoyl; vinylsulfonyl; acrylamido; phthalimidinyl; benzoylsulfonicimidyl; alkylsulfonamido; phenylsulfonamido; alkoxycarbonylamino; alkylcarbamoyloxy; alkoxycarbonyl; alkoxycarbonyloxy; ##STR6## wherein Y is --NH--, --NH-alkyl--, --O--, --S--, or --CH₂ O--; --S--R⁶ wherein R⁶ is alkyl, phenyl, phenyl substituted with halogen, alkyl, alkoxy, alkanoylamino, cyano, or alkoxycarbonyl, pyridyl, pyrimidinyl, benzoxazolyl, benzimidazolyl, benzothiazolyl, triazolyl, or ##STR7## --SO₂ R³ ; --COOR³ ; --OXR³ ; --NH--X--R³ ; --X--R³ ; --OCO--R³ ; --CONR⁷ R⁷ ; --SO₂ NR⁷ R⁷ ; wherein R³ and X are as defined above and each R⁷ is selected from H and R³ ; alkoxy; alkoxy substituted with hydroxy, cyano, alkanoyloxy, or alkoxy; phenoxy or phenoxy substituted with one or more of alkyl, alkoxy or halogen. All of the aliphatic portions of the various groups herein contain from 1-6 carbons, and are straight or branched chain.

The dyes of this invention impart red to blue shades on fibers, particularly polyamides, and are especially useful for dyeing polyamide (nylon) carpets, giving good fastness to light ozone, oxides of nitrogen, washing, sublimation, crocking and the like, and having good leveling, transfer, exhaustion, and build properties.

The couplers used in this invention are prepared according to known procedures. The dyes may be prepared by reacting the coupler with a diazonium salt which contains one or two carbalkoxy groups. The product is reacted first with an aminoalcohol H--X'--Z--OH (X' is NH, Z is alkylene) to convert to a N-(hydroxyalkyl)carbamyl group, or with an alkanediol H--X'--Z--OH (X' is O, Z is alkylene) to convert to a hydroxyalkoxycarbonyl group. Subsequently, the material is reacted with concentrated sulfuric acid to form the sulfate ester: ##STR8## Alternatively, a diazotizable amine containing a hydroxyalkoxycarbonyl group or a N-(hydroxyalkyl)carbamyl group may be sulfated before diazotization and coupling:

This invention will be further illustrated by the following examples although it will be understood that these examples are included merely for purposes of illustration and are not intended to limit the scope of the invention. The compounds listed in the tables below can be prepared by procedures well known in the art. In these tables, the "Position" column refers to the position of the ##STR10## group or groups on the pyrazol-5-yl ring.

                                      TABLE 1                                      __________________________________________________________________________      ##STR11##                                                                     Posi-                                                                          tion                                                                              R       R.sup.1                                                                               R.sup.2    R.sup.4  R.sup.5   X'Z         M                  __________________________________________________________________________     3  H       H      2-CH.sub.3, 5-NHCOCH.sub.3                                                                H        C.sub.2 H.sub.5                                                                          NHC.sub.2 H.sub.4                                                                          Na                 "  H       4-CH.sub.3                                                                            H          C.sub.2 H.sub.5                                                                         C.sub.2 H.sub.4 N(COCH.sub.3).sub.2                                                      N(CH.sub.3)C.sub.2                                                             H.sub.4     "                  "  H       4-C.sub.6 H.sub.5                                                                     3-CH.sub.3 C.sub.2 H.sub.4 Cl                                                                      C.sub.2 H.sub.4 CN                                                                       NHC.sub.2 H.sub.4                                                                          K                  "  CH.sub.3                                                                               4-CH.sub.3                                                                            "          "                  NHCH.sub.2CH(C.sub.6                                                           H.sub.5)    K                  "  C.sub.6 H.sub.4p-Br                                                                    H      3-CH.sub.3 C.sub.2 H.sub.4 OH                                                                      C.sub.2 H.sub.4 OH                                                                       OC.sub.2 H.sub.4                                                                           Na                 "  "       4-CH.sub.2 CN                                                                         3-NHCOCH.sub.3                                                                            C.sub.2 H.sub.5                                                                         C.sub.2 H.sub.4 CN                                                                       NHC.sub.2 H.sub.4                                                              OC.sub.2 H.sub.4                                                                           Na                 "  SO.sub.2 C.sub.6 H.sub.5                                                               4-C.sub.6 H.sub.5                                                                     2-OCH.sub.3, 5-NHCOCH.sub.3                                                               C.sub.2 H.sub.4 OCOCH.sub.3                                                             C.sub.2 H.sub.4 OCOCH.sub.3                                                              NHC.sub.2 H.sub.4                                                                          NH.sub.4           4  H       3-CONH.sub.2                                                                          3-Cl       C.sub.2 H.sub.4 OH                                                                      C.sub.6 H.sub.13                                                                         OC.sub.2 H.sub.4                                                                           K                  "  H       H      2-Cl       H        C.sub.2 H.sub.4 OH                                                                       OC.sub.2 H.sub.4                                                                           K                  "  H       3-CONH.sub.2                                                                          2-CH.sub.3, 3-Cl                                                                          H        CH.sub.2 C.sub.6 H.sub.5                                                                 NHC.sub.3 H.sub.6                                                                          K                  "  H       H      H          C.sub.2 H.sub.4 OH                                                                      C.sub.2 H.sub.4 CN                                                                       OC.sub.2 H.sub.4                                                                           NH.sub.4           "  CH.sub.3                                                                               H      H          C.sub.2 H.sub.4 OSO.sub.3 K                                                             C.sub.2 H.sub.5                                                                          NHC.sub.2 H.sub.4                                                                          K                  "  "       3-CH.sub.3                                                                            3-CH.sub.3 C.sub.2 H.sub.5                                                                         C.sub.2 H.sub.4 NHCOCH.sub.3                                                             "           "                  "  SCN     3-C.sub.6 H.sub.5                                                                     3-NHCOCH.sub.3                                                                            "        C.sub.2 H.sub.4 CONH.sub.2                                                               "           "                  "  C.sub.2 H.sub.4 OCH.sub.3                                                              3-CH.sub.3                                                                            H          "        C.sub.2 H.sub.4 NHCOCH.sub.3                                                             N(C.sub.6 H.sub.5)C.sub.2                                                      H.sub.4     Na                 "  C.sub.2 H.sub.4 CN                                                                     3-COCH.sub.3                                                                          "          "        H         NHC.sub.2 H.sub.4              "  C.sub.6 H.sub.5                                                                        3-C.sub.6 H.sub.5                                                                     H          CH.sub.2 CH.sub.2OCH.sub.2 CH.sub.2                                                               NHC.sub.2 H.sub.4                                                                          Na                 "  "       H      H          CH.sub.2 CH.sub.2SCH.sub.2 CH.sub.2                                                               NHC.sub.2 H.sub.4                                                                          Na                 "  "       3-CONHCH.sub.3                                                                        H          CH.sub.2 CH.sub.2SO.sub.2CH.sub.2 CH.sub.2                                                        NHC.sub.2 H.sub.4                                                                          Na                 "  "       3-CH.sub.3                                                                            H          CH.sub.2 CH.sub.2NHCH.sub.2 CH.sub.2                                                              NHC.sub.2 H.sub.4                                                                          Na                 "  "       3-C.sub.2 H.sub.4 Cl                                                                  H          CH.sub.2 CH.sub.2N(COCH.sub.3)CH.sub.2                                         CH.sub.2           NHC.sub.2 H.sub.4                                                                          Na                 "  "       3-Br   3-CH.sub.3 H        C.sub.2 H.sub.4 SO.sub.2 NH.sub.2                                                        NHC.sub.2 H.sub.4                                                                          Na                 "  C.sub.6 H.sub.4p-OCH.sub.3                                                             "      2-OC.sub.6 H.sub.5                                                                        C.sub.2 H.sub.4 CN                                                                      C.sub.2 H.sub.4 N(COCH.sub.3).sub.2                                                      NHC.sub.2 H.sub.4                                                                          "                  "  "       3-CONH.sub.2                                                                          2-SCH.sub.3                                                                               C.sub.2 H.sub.4 OCOCH.sub.3                                                             C.sub.2 H.sub.4 SO.sub.2 NHC.sub.2                                             H.sub.5   NHC.sub.2 H.sub.4                                                                          K                  "  C.sub.6 H.sub.4p-Br                                                                    3-CH.sub.2 CN                                                                         3-SC.sub.6 H.sub.5                                                                        CONH.sub.2                                                                              C.sub.2 H.sub.4 SO.sub.2 NHC.sub.2                                             H.sub.5   NHCH.sub.2CH(C.sub.6                                                           H.sub.5)    K                  "  SO.sub.2 CH.sub.3                                                                      3-CH.sub.2 CN                                                                         3-NHCOOCH.sub.3                                                                           C.sub.2 H.sub.4 OH                                                                      C.sub.2 H.sub.4 OH                                                                       OC.sub.2 H.sub.4                                                                           Na                 "  SO.sub.2 NHCH.sub.3                                                                    3-C.sub.6 H.sub.5                                                                     3-NHSO.sub.2 CH.sub.3                                                                     C.sub.2 H.sub.5                                                                         C.sub.2 H.sub.4 CN                                                                       NHC.sub.2 H.sub.4                                                              OC.sub.2 H.sub.4                                                                           Na                 "  SO.sub.2 C.sub.6 H.sub.5                                                               H      2-OCH.sub.3, 5-NHCOCH.sub.3                                                               C.sub.2 H.sub.4 OCOCH.sub.3                                                             C.sub.2 H.sub.4 OCOCH.sub.3                                                              NHC.sub.2 H.sub.4                                                                          NH.sub.4           "  "       3-CH.sub.3                                                                            3-NHCOCH.sub.2 Cl                                                                         C.sub.2 H.sub.4 OH                                                                      C.sub.6 H.sub.13                                                                         OC.sub.2 H.sub.4                                                                           K                  "  COCH.sub.3                                                                             3-C.sub.6 H.sub.5                                                                     3-NHCOC.sub.2 H.sub.4 OH                                                                  H        C.sub.2 H.sub.4 OH                                                                       OC.sub.2 H.sub.4                                                                           K                  3,4                                                                               H              2-CH.sub.3, 3-Cl                                                                          H        CH.sub.2 C.sub.6 H.sub.5                                                                 NHC.sub.3 H.sub.6                                                                          K                  "  H       H      2-NHCON(C.sub.2 H.sub.5).sub.2                                                            C.sub.2 H.sub.4 OH                                                                      C.sub.2 H.sub.4 CN                                                                       OC.sub.2 H.sub.4                                                                           NH.sub.4           "  CH.sub.3                                                                               H      2-NHCON(C.sub.2 H.sub.5)                                                                  C.sub.2 H.sub.4 OSO.sub.3 K                                                             C.sub.2 H.sub.5                                                                          NHC.sub.2 H.sub.4                                                                          K                  "  C.sub.2 H.sub.4 OCH.sub.3                                                              H      3-CH.sub.3 C.sub.2 H.sub.5                                                                         C.sub.2 H.sub.4 NHCOCH.sub.3                                                             NHC.sub.2 H.sub.4                                                                          "                  "  C.sub.6 H.sub.4p-CN                                                                    H      3-NHCOCH.sub.3                                                                            "        C.sub.2 H.sub.4 CONH.sub.2                                                               NHC.sub.2 H.sub.4                                                                          "                  "  "       H      H          "        C.sub.2 H.sub.4 NHCOCH.sub.3                                                             NHC.sub.2 H.sub.4                                                                          Na                 __________________________________________________________________________

                                      TABLE 2                                      __________________________________________________________________________      ##STR12##                                                                     Posi-                                                                          tion                                                                              R       R.sup.1 R.sup.2   R.sup.8 R.sup.4    X'Z         M                  __________________________________________________________________________     3  H       H       7-CH.sub.3                                                                               2-CH.sub.3                                                                             C.sub.2 H.sub.4 OH                                                                        OC.sub.2 H.sub.4                                                                           Na                 "  H       4-CH.sub.3                                                                             7-CH.sub.3                                                                               2-CH.sub.3                                                                             C.sub.2 H.sub.4 OSO.sub.3 K                                                               NHC.sub.2 H.sub.4                                                                          K                  "  H       4-C.sub.6 H.sub.5                                                                      H         H       C.sub.2 H.sub.4 OC.sub.6 H.sub.11                                                         OC.sub.2 H.sub.4                                                                           Na                 "  CH.sub.3                                                                               4-CH.sub.3                                                                             5-CH.sub.3                                                                               H       C.sub. 4 H.sub.9                                                                          NHC.sub.2 H.sub.4                                                                          Na                 "  C.sub.6 H.sub.4p-Br                                                                    H       7-CH.sub.3                                                                               2-CH.sub.3                                                                             C.sub.2 H.sub.4 NHCOCH.sub.3                                                              "           "                  "  "       4-CH.sub.2 CN                                                                          7-CH.sub.3                                                                               2,2,4-(CH.sub.3).sub.3                                                                 "          N(C.sub.2 H.sub.5)C.sub.2                                                      H.sub.4     "                  "  SO.sub.2 C.sub.6 H.sub.5                                                               4-C.sub.6 H.sub.5                                                                      8-CH.sub.3                                                                               H       C.sub.2 H.sub.4 Cl                                                                        OC.sub.2 H.sub.4                                                                           NH.sub.4           4  H       3-CONH.sub.2                                                                           H         2,2,4-(CH.sub.3).sub.3                                                                 C.sub.2 H.sub.4 OCH.sub.3                                                                 OC.sub.2 H.sub.4 OC.sub.2                                                      H.sub.4     K                  "  H       H       7-NHCOCH.sub.3                                                                           "       C.sub.2 H.sub.4 Br                                                                        NHC.sub.2 H.sub.4                                                                          K                  "  H       3-CONH.sub.2                                                                           "         5-CH.sub.3                                                                             CH.sub.2 CHOHCH.sub.2 OH                                                                  OC.sub.2 H.sub.4                                                                           K                  "  H       H       7-CH.sub.3                                                                               2-CH.sub.3                                                                             CH.sub.3   NHC.sub.2 H.sub.4                                                                          K                  "  CH.sub.3                                                                               H       7-C.sub.6 H.sub.11                                                                       3-OH    C.sub.2 H.sub.4 SO.sub.2 NH.sub.2                                                         NHC.sub.2 H.sub.4                                                                          Na                 "  "       3-CH.sub.3                                                                             7-OC.sub.6 H.sub.5                                                                       3-CN    C.sub.2 H.sub.4 N(COCH.sub.                                                               N(C.sub.6 H.sub.5)C.sub.2                                                      H.sub.4     "                  "  SCN     3-C.sub.6 H.sub.5                                                                      7-SCH.sub.3                                                                              3-OCOCH.sub.3                                                                          C.sub.2 H.sub.4 SO.sub.2 NHC.sub.2                                             H.sub.5    NHC.sub.2 H.sub.4                                                                          K                  3  C.sub.6 H.sub.5                                                                        H       7-CH.sub.3                                                                               2-CH.sub.3                                                                             C.sub.2 H.sub.5                                                                           NHC.sub.2 H.sub.4                                                                          Na                 4  C.sub.2 H.sub.4 OCH.sub.3                                                              3-CH.sub.3                                                                             7-SC.sub.6 H.sub.5                                                                       2-CH.sub.3                                                                             C.sub.2 H.sub.4 SO.sub.2 NHC.sub.2                                             H.sub.5    NHCH.sub.2CH(C.sub.6                                                           H.sub.5)    K                  "  C.sub.2 H.sub.4 CN                                                                     3-COCH.sub.3                                                                           7-NHCOOCH.sub.3                                                                          "       C.sub.2 H.sub.4 OH                                                                        OC.sub.2 H.sub.4                                                                           Na                 "  C.sub.6 H.sub.5                                                                        3-C.sub.6 H.sub.5                                                                      7-NHSO.sub.2 CH.sub.3                                                                    2-C.sub.2 H.sub.5                                                                      C.sub.2 H.sub.4 CN                                                                        NHC.sub.2 H.sub.4                                                              OC.sub.2 H.sub.4                                                                           Na                 "  "       H       7-OCH.sub.3                                                                              3-OCOCH.sub.3                                                                          C.sub.2 H.sub.4 OCOCH.sub.3                                                               NHC.sub.2 H.sub.4                                                                          NH.sub.4           "  "       3-CONHCH.sub.3                                                                         7-NHCOCH.sub.2 Cl                                                                        3-OH    C.sub.6 H.sub.13                                                                          OC.sub.2 H.sub.4                                                                           K                  "  "       3-CH.sub.3                                                                             7-NHCOC.sub.2 H.sub.4 OH                                                                 3-CONH.sub.2                                                                           C.sub.2 H.sub.4 OH                                                                        OC.sub.                                                                                    K H.sub.4          "  "       3-C.sub.2 H.sub.4 Cl                                                                   7-CH.sub.3, 5-Cl                                                                         3-Cl    CH.sub.2 C.sub.6 H.sub.5                                                                  NHC.sub.3 H.sub.6                                                                          K                  "  "       3-Br    7-NHCONHC.sub.2 H.sub.5                                                                  3-OC.sub.6 H.sub.5                                                                     C.sub.2 H.sub.4 CN                                                                        OC.sub.2 H.sub.4                                                                           NH.sub.4           "  C.sub.6 H.sub.4p-OCH.sub.3                                                             "       7-NHCON(C.sub.2 H.sub.5).sub.2                                                           3-OC.sub.6 H.sub.5                                                                     C.sub.2 H.sub.5                                                                           NHC.sub.2 H.sub.4                                                                          K                  "  "       3-CONH.sub.2                                                                           7-CH.sub.3                                                                               3-SC.sub.2 H.sub.5                                                                     C.sub.2 H.sub.4 NHCOCH.sub.3                                                              "           "                  "  C.sub.6 H.sub.4p-Br                                                                    3-CH.sub.2 CN                                                                          7-NHCOCH.sub.3                                                                           3-CONHC.sub.2 H.sub.5                                                                  C.sub.2 H.sub.4 CONH.sub.2                                                                "           "                  "  SO.sub.2 CH.sub.3                                                                      3-CH.sub.2 CN                                                                          H         3-OCH.sub.3                                                                            C.sub.2 H.sub.4 NHCOCH.sub.3                                                              "           Na                 __________________________________________________________________________

                                      TABLE 3                                      __________________________________________________________________________      ##STR13##                                                                     Posi-                                                                          tion                                                                              R       R.sup.1                                                                               R.sup.2   R.sup.8  R.sup.4   X'Z          M                  __________________________________________________________________________     3  H       H      6-NHCOCH.sub.3                                                                           3-CH.sub.3                                                                              C.sub.2 H.sub.5                                                                          NHC.sub.2 H.sub.4                                                                           Na                 "  H       4-CH.sub.3                                                                            6-CH.sub.3                                                                               3-CH.sub.3                                                                              C.sub.2 H.sub.5                                                                          OC.sub.2 H.sub.4                                                                            Na                 "  H       4-C.sub.6 H.sub.5                                                                     6-Cl      "        C.sub.2 H.sub.4 OH                                                                       OC.sub.2 H.sub.4                                                                            K                  "  CH.sub.3                                                                               4-CH.sub.3                                                                            6-Br      2,3-di-CH.sub.3                                                                         C.sub.2 H.sub.4 SO.sub.2 NH.sub.2                                                        "            NH.sub.4           "  C.sub.6 H.sub.4p-Br                                                                    H      6-F       3-CH.sub.3                                                                              "         NHC.sub.2 H.sub.4                                                                           K                  "  "       4-CH.sub.2 CN                                                                         H         2-CH.sub.2 OH                                                                           CH(CH.sub.3).sub.2                                                                       "            "                  "  SO.sub.2 C.sub.6 H.sub.5                                                               4-C.sub.6 H.sub.5                                                                     H         2-CH.sub.2 OH                                                                           "         N(CH.sub.3)C.sub.2                                                                          ".sub.4            4  H       3-CONH.sub.2                                                                          6-NHCOCH.sub.3                                                                           2-CH.sub.2 Cl                                                                           C.sub.2 H.sub.5                                                                          NHC.sub.3 H.sub.6                                                                           Na                 "  H       H      "         3-CH(CH.sub.3).sub.2                                                                    C.sub.2 H.sub.4 OCH.sub.3                                                                NHC.sub.2 H.sub.4                                                                           Na                 "  H       3-CONH.sub.2                                                                          6-CH.sub.3                                                                               3-CH.sub.3                                                                              "         "            Na                 "  H       H      6-C.sub.6 H.sub.11                                                                       2-CH.sub.2 OC.sub.6 H.sub.5                                                             C.sub.2 H.sub.4 SO.sub.2 NH.sub.2                                                        NHC.sub.2 H.sub.4                                                                           Na                 "  CH.sub.3                                                                               H      6-OC.sub.6 H.sub.5                                                                       2-CH.sub.2 OC.sub.2 H.sub.5                                                             C.sub.2 H.sub.4 N(COCH.sub.3).sub.2                                                      "            "                  "  "       3-CH.sub.3                                                                            6-SCH.sub.3                                                                               ##STR14##                                                                              C.sub.2 H.sub. 4 SO.sub.2 NHC.sub.2                                            H.sub.5   NHC.sub.2 H.sub.4                                                                           K                  "  SCN     3-C.sub.6 H.sub.5                                                                     6-SC.sub.6 H.sub.5                                                                       2-CH.sub.2 Cl                                                                           C.sub.2 H.sub.4 SO.sub.2 NHC.sub.2                                             H.sub.5   NHCH.sub.2CH(C.sub.6                                                           H.sub.5)     K                  "  C.sub.2 H.sub.4 OCH.sub.3                                                              3-CH.sub.3                                                                            6-NHCOOCH.sub.3                                                                          2-CH.sub.2 OH                                                                           C.sub.2 H.sub.4 OH                                                                       OC.sub.2 H.sub.4                                                                            Na                 "  C.sub.2 H.sub.4 CN                                                                     3-COCH.sub.3                                                                          6-NHSO.sub.2 CH.sub.3                                                                    "        C.sub.2 H.sub.4 CN                                                                       NHC.sub.2 H.sub.4 OC.sub.2                                                     H.sub.4      Na                 "  C.sub.6 H.sub.5                                                                        3-C.sub.6 H.sub.5                                                                     8-OCH.sub.3                                                                               ##STR15##                                                                              C.sub.2 H.sub.4 OCOCH.sub.3                                                              NHC.sub.2 H.sub.4                                                                           NH.sub.4           "  "       H      5-NHCOCH.sub.3                                               "  "       3-CONHCH.sub.3                                                                        6-NHCOCH.sub.2 Cl                                                                        "        C.sub.6 H.sub.13                                                                         OC.sub.2 H.sub.4                                                                            K                  "  "       3-CH.sub.3                                                                            6-NHCOC.sub.2 H.sub.4 OH                                                                 3-C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.4 OH                                                                       OC.sub.2 H.sub.4                                                                            K                  "  "       3-C.sub.2 H.sub.4 Cl                                                                  8-CH.sub.3, 5-Cl                                                                         "        CH.sub.2 C.sub.6 H.sub.5                                                                 NHC.sub.3 H.sub.6                                                                           K                  "  "       3-Br   6-NHCONHC.sub.2 H.sub.5                                                                  2-CH.sub.2 OC.sub.6 H.sub.5                                                             C.sub.2 H.sub.4 CN                                                                       OC.sub.2 H.sub.4                                                                            NH.sub.4           "  C.sub.6 H.sub.4p-OCH.sub.3                                                             "      6-NHCON(C.sub.2 H.sub.5).sub.2                                                           2-CH.sub.2 OC.sub.6 H.sub.5                                                             C.sub.2 H.sub.5                                                                          NHC.sub.2 H.sub.4                                                                           K                  "  "       3-CONH.sub.2                                                                          6-OC.sub.6 H.sub.5                                                                       H        C.sub.2 H.sub.4 NHCOCH.sub.3                                                             "            "                  "  C.sub.6 H.sub.4p-Br                                                                    3-CH.sub.2 CN                                                                         6-NHCOCH.sub.3                                                                           "        C.sub.2 H.sub.4 CONH.sub.2                                                               "            "                  "  SO.sub.2 CH.sub.3                                                                      3-CH.sub.2 CN                                                                         H         "        C.sub.2 H.sub.4 NHCOCH.sub.3                                                             N(C.sub.6 H.sub.5)C.sub.2                                                      H.sub.4      Na                 __________________________________________________________________________

                                      TABLE 4                                      __________________________________________________________________________      ##STR16##                                                                     Posi-                                                                          tion                                                                               R       R.sup.1                                                                               R.sup.9  R.sup.2   R.sup.4  X'Z         M                   __________________________________________________________________________     3   H       H      C.sub.6 H.sub.5                                                                         H         CH.sub.3 NHC.sub.2 H.sub.4                                                                          Na                  "   H       4-CH.sub.3                                                                            CH.sub.3 6-CH.sub.3                                                                               CH.sub.3 "           "                   "   H       4-C.sub.6 H.sub.5                                                                     "        "         C.sub.6 H.sub.5                                                                         "           "                   "   CH.sub.3                                                                               4-CH.sub.3                                                                            "        H         C.sub.2 H.sub.5                                                                         "           "                   "   C.sub.6 H.sub.4 p-Br                                                                   H      C.sub.6 H.sub.5                                                                         H         H        "           "                   "   "       4-CH.sub.2 CN                                                                         "        "         CH.sub.3 "           "                   "   SO.sub.2 C.sub.6 H.sub.5                                                               4-C.sub.6 H.sub.5                                                                     CH.sub.3 "         CH.sub.3 N(CH.sub.3)C.sub.2                                                                         ".sub.4             4   H       3-CONH.sub.2                                                                          "        5-OC.sub.2 H.sub.5                                                                       "        NHC.sub.3 H.sub.6                                                                          "                   "   H       H      CH.sub.3 "         H        NHC.sub.2 H.sub.4                                                                          "                   "   H       3-CONH.sub.2                                                                          C.sub.6 H.sub.4p-Br                                                                     H         H        "           "                   "   H       H      C.sub.6 H.sub.5                                                                         "         C.sub.2 H.sub.4 CONH.sub.2                                                              "           K                   "   CH.sub.3                                                                               H      C.sub.6 H.sub.4p-OCH.sub.3                                                              "         C.sub.2 H.sub.4 CN                                                                      N(C.sub.6 H.sub.5)C.sub.2                                                      H.sub.4     K                   "   "       3-CH.sub.3                                                                            "        5-C.sub.6 H.sub.11                                                                       C.sub.2 H.sub.4 SO.sub.2 NH.sub.2                                                       NHC.sub.2 H.sub.4                                                                          "                   "   SCN     3-C.sub.6 H.sub.5                                                                     C.sub.2 H.sub.4 CN                                                                      6-OC.sub.6 H.sub.5                                                                       C.sub.2 H.sub.4 N(COCH.sub.3).sub.2                                                     "           "                   "   C.sub.2 H.sub.4 OCH.sub.3                                                              3-CH.sub.3                                                                            C.sub.2 H.sub.4 OCOCH.sub.3                                                             6-SCH.sub.3                                                                              C.sub.2 H.sub.4 SO.sub.2 NHC.sub.2                                             H.sub.5  NHC.sub.2 H.sub.4                                                                          K                   "   C.sub.2 H.sub.4 CN                                                                     3-COCH.sub.3                                                                          CH.sub.3 6-SC.sub.6 H.sub.5                                                                       C.sub.2 H.sub.4 SO.sub.2 NHC.sub.2                                             H.sub.5  NHCH.sub.2CH(C.sub.6                                                           H.sub.5)    K                   "   C.sub.6 H.sub.5                                                                        3-C.sub.6 H.sub.5                                                                     "        6-NHCOOCH.sub.3                                                                          C.sub.2 H.sub.4 OH                                                                      OC.sub.2 H.sub.4                                                                           Na                  "   "       H      C.sub.3 H.sub.7                                                                         6-NHSO.sub.2 CH.sub.3                                                                    C.sub.2 H.sub.4 CN                                                                      NHC.sub.2 H.sub.4 OC.sub.2                                                     H.sub.4     Na                  "   "       3-CONHCH.sub.3                                                                        CH.sub.3 6-OCH.sub.3,                                                                             C.sub.2 H.sub.4 OCOCH.sub.3                                                             NHC.sub.2 H.sub.4                                                                          NH.sub.4                                        5-NHCOCH.sub.3                                     "   "       3-CH.sub.3                                                                            C.sub.2 H.sub.5                                                                         6-NHCOCH.sub.2 Cl                                                                        C.sub.6 H.sub.13                                                                        OC.sub.2 H.sub.4                                                                           K                   "   "       3-C.sub.2 H.sub.4 Cl                                                                  "        6-NHCOC.sub.2 H.sub.4 OH                                                                 C.sub.2 H.sub.4 OH                                                                      OC.sub.2 H.sub.4                                                                           K                   "   "       3-Br   "        "         CH.sub.2 C.sub.6 H.sub.5                                                                NHC.sub.3 H.sub.6                                                                          K                   "   C.sub.6 H.sub.4p-OCH.sub.3                                                             "      C.sub.2 H.sub.5                                                                         6-NHCONHC.sub.2 H.sub.5                                                                  C.sub.2 H.sub.4 CN                                                                      OC.sub.2 H.sub.4                                                                           NH.sub.4            "   "       3-CONH.sub.2                                                                          C.sub.6 H.sub.4p-OCH.sub.3                                                              6-NHCON(C.sub.2 H.sub.5).sub.2                                                           C.sub.2 H.sub.5                                                                         NHC.sub.2 H.sub.4                                                                          K                   "   C.sub.6 H.sub.4p-Br                                                                    3-CH.sub.2 CN                                                                         C.sub.2 H.sub.5                                                                         6-CH.sub.3                                                                               C.sub.2 H.sub.4 NHCOCH.sub.3                                                            "           "                   "   SO.sub.2 CH.sub.3                                                                      3-CH.sub.2 CN                                                                         C.sub.2 H.sub.5                                                                         6-NHCOCH.sub.3                                                                           C.sub.2 H.sub.4 CONH.sub.2                                                              "           "                   "   SO.sub.2 NHCH.sub.3                                                                    3-C.sub.6 H.sub.5                                                                     CH.sub.3 H         C.sub.2 H.sub.4 NHCOCH.sub.3                                                            "           Na                  "   SO.sub.2 C.sub.6 H.sub.5                                                               H      "        "         C.sub.2 H.sub.4 Cl                                                                      "           "                   "   "       3-CH.sub.3                                                                            C.sub.6 H.sub.4p-CH.sub.3                                                               6-OH      "        "           "                   __________________________________________________________________________

                                      TABLE 5                                      __________________________________________________________________________      ##STR17##                                                                     Posi-                                                                          tion                                                                              R       R.sup.1                                                                               R.sup.9 R.sup.10 X'Z         M                               __________________________________________________________________________     3  H       H      C.sub.6 H.sub.5                                                                        H        NHC.sub.2 H.sub.4                                                                          Na                              "  H       4-CH.sub.3                                                                            CH.sub.3                                                                               "        OC.sub.2 H.sub.4 OC.sub.2 H.sub.4                                                          Na                              "  H       4-C.sub.6 H.sub.5                                                                     CH.sub.3                                                                               H        OC.sub.2 H.sub.4                                                                           Na                              "  CH.sub.3                                                                               4-CH.sub.3                                                                            CH.sub.3                                                                               C.sub.6 H.sub.5                                                                         NHC.sub.2 H.sub.4                                                                          Na                              "  C.sub.6 H.sub.4p-Br                                                                    H      CH.sub.3                                                                               C.sub. 6 H.sub.5                                                                        NHC.sub.3 H.sub.6                                                                          Na                              "  "       4-CH.sub.2 CN                                                                         C.sub.6 H.sub.5                                                                        CH.sub.3 NHC.sub.2 H.sub.4                                                                          Na                              "  SO.sub.2 C.sub.6 H.sub.5                                                               4-C.sub.6 H.sub.5                                                                     C.sub.6 H.sub.5                                                                        "        "           NH.sub.4                        4  H       3-CONH.sub.2                                                                          "       "        N(C.sub.2 H.sub.5)C.sub.2 H.sub.4                                                          "                               "  H       H      CH.sub.3                                                                               H        NHC.sub.2 H.sub.4                                                                          K                               "  H       3-CONH.sub.2                                                                          "       H        NH(CH.sub.2).sub.5                                                                         K                               "  H       H      C.sub.6 H.sub.4p-Br                                                                    "        OC.sub.2 H.sub.4                                                                           K                               "  CH.sub.3                                                                               H      C.sub.6 H.sub.4p-OCH.sub.3                                                             "        OC.sub.2 H.sub.4 OC.sub.2 H.sub.4                                                          K                               "  "       3-CH.sub.3                                                                            "       Br       NHC.sub.2 H.sub.4                                                                          K                               "  SCN     3-C.sub.6 H.sub.5                                                                     C.sub.2 H.sub.4 CN                                                                     Br       N(C.sub.6 H.sub.5)C.sub.2 H.sub.4                                                          K                               "  C.sub.2 H.sub.4 OCH.sub.3                                                              3-CH.sub.3                                                                            C.sub.2 H.sub.4 OCOCH.sub.3                                                            Br       NHC.sub.2 H.sub.4                                                                          K                               "  C.sub.2 H.sub.4 CN                                                                     3-COCH.sub.3                                                                          CH.sub. 3                                                                              C.sub.2 H.sub.5                                                                         NHCH.sub.2CH(C.sub.6 H.sub.5)                                                              K                               "  C.sub.6 H.sub.5                                                                        3-C.sub.6 H.sub.5                                                                     "       C.sub.2 H.sub.5                                                                         OC.sub.2 H.sub.4                                                                           K                               "  "       H      C.sub.3 H.sub.7                                                                        C.sub.6 H.sub.5                                                                         NHC.sub.2 H.sub.4 OC.sub.2 H.sub.4                                                         K                               "  "       3-CONHCH.sub.3                                                                        CH.sub.3                                                                               "        NHC.sub.2 H.sub.4                                                                          K                               "  "       3-CH.sub.3                                                                            C.sub.2 H.sub.5                                                                        C.sub.6 H.sub.4p-CH.sub.3                                                               OC.sub.2 H.sub.4                                                                           K                               "  "       3-C.sub.2 H.sub.4 Cl                                                                  "       H        OC.sub.2 H.sub.4                                                                           K                               "  "       3-Br   "       CONHC.sub.2 H.sub.5                                                                     NHC.sub.3 H.sub.6                                                                          K                               "  C.sub.6 H.sub.4p-OCH.sub.3                                                             "      C.sub.2 H.sub.5                                                                        CH.sub.3 OC.sub.2 H.sub.4                                                                           K                               "  "       3-CONH.sub.2                                                                          C.sub.6 H.sub.4p-OCH.sub.3                                                             C.sub.2 H.sub.5                                                                         NHC.sub.2 H.sub.4                                                                          K                               "  C.sub.6 H.sub.4p-Br                                                                    3-CH.sub.2 CN                                                                         C.sub.2 H.sub.5                                                                        SCN      "           K                               "  SO.sub.2 CH.sub.3                                                                      3-CH.sub.2 CN                                                                         C.sub.2 H.sub.5                                                                        CONH.sub.2                                                                              "           K                               "  SO.sub.2 NHCH.sub.3                                                                    3-C.sub.6 H.sub.5                                                                     CH.sub.3                                                                               CH(CH.sub.3).sub.2                                                                      "           K                               "  SO.sub.2 C.sub.6 H.sub.5                                                               H      "       C.sub.6 H.sub.5                                                                         "           K                               "  "       3-CH.sub.3                                                                            C.sub.6 H.sub.4p-CH.sub.3                                                              C.sub.2 H.sub.5                                                                         NHC.sub.2 H.sub.4 OCH.sub.2                                                                K                               __________________________________________________________________________

                                      TABLE 6                                      __________________________________________________________________________      ##STR18##                                                                     Posi-                                                                          tion                                                                              R       R.sup.1                                                                               R.sup.4  R.sup.11    X'Z         M                           __________________________________________________________________________     3  H       H      H        CH.sub.3    NHC.sub.2 H.sub.4                                                                          K                           "  H       4-CH.sub.3                                                                            H        C.sub.6 H.sub.4p-OCH.sub.3                                                                 "           "                           "  H       4-C.sub.6 H.sub.5                                                                     H        CF.sub.3    "           "                           "  CH.sub.3                                                                               4-CH.sub.3                                                                            H        COOC.sub.2 H.sub.5                                                                         "           "                           "  C.sub.6 H.sub.4p-Br                                                                    H      H                                                                                        ##STR19##  "           Na                          "  "       4-CH.sub.2 CN                                                                         H        C.sub.6 H.sub.5                                                                            "           K                           "  SO.sub.2 C.sub.6 H.sub.5                                                               4-C.sub.6 H.sub.5                                                                     C.sub.6 H.sub.5                                                                         C.sub.6 H.sub.4p-Br                                                                        "           "                           4  H       3-CONH.sub.2                                                                          "        C(CH.sub.3).sub.3                                                                          "           "                           "  H       H      "        C.sub.6 H.sub.11                                                                           "           Na                          "  H       3-CONH.sub.2                                                                          "        C.sub.6 H.sub.5                                                                            "           Na                          "  H       H      C.sub.6 H.sub.5 SO.sub.2                                                                CH.sub.3    N(CH.sub.3)C.sub.2 H.sub.4                                                                 Na                          "  CH.sub.3                                                                               H      C.sub.2 H.sub.5 SO.sub.2                                                                "           NHC.sub.2 H.sub.4                                                                          K                           "  "       3-CH.sub.3                                                                             ##STR20##                                                                              "           N(C.sub.6 H.sub.5)C.sub.2 H.sub.4                                                          K                           "  SCN     3-C.sub.6 H.sub.5                                                                      ##STR21##                                                                              CH.sub.3    NHC.sub.2 H.sub.4                                                                          K                           "  C.sub.2 H.sub.4 OCH.sub.3                                                              3-CH.sub.3                                                                            CH.sub.3 CONH.sub.2  NHCH.sub.2CH(C.sub.6 H.sub.5)                                                              K                           "  C.sub.2 H.sub.4 CN                                                                     3-COCH.sub.3                                                                          C.sub.2 H.sub.4 OH                                                                      C.sub.2 H.sub.5                                                                            OC.sub.2 H.sub.4                                                                           K                           "  C.sub.6 H.sub.5                                                                        3-C.sub.6 H.sub.5                                                                     C.sub.2 H.sub.4 CN                                                                      "           NHC.sub.2 H.sub.4 OC.sub.2                                                                 K.sub.4                     "  "       H      C.sub.2 H.sub.4 OCOCH.sub.3                                                             "           NHC.sub.2 H.sub.4                                                                          K                           "  "       3-CONHCH.sub.3                                                                        C.sub.6 H.sub.11                                                                        CF.sub.3    OC.sub.2 H.sub.4                                                                           K                           "  "       3-CH.sub.3                                                                            C.sub.2 H.sub.4 OH                                                                      C.sub.6 H.sub.4p-Cl                                                                        OC.sub.2 H.sub.4                                                                           K                           "  "       3-C.sub.2 H.sub.4 Cl                                                                  CH.sub.2 C.sub.6 H.sub.5                                                                CONHC.sub.2 H.sub.5                                                                        NHC.sub.3 H.sub.6                                                                          K                           "  "       3-Br   C.sub.2 H.sub.4 CN                                                                      CH(CH.sub.3).sub.2                                                                         OC.sub.2 H.sub.4                                                                           K                           "  C.sub.6 H.sub.4p-OCH.sub.3                                                             "      C.sub.2 H.sub.5                                                                         "           NHC.sub.2 H.sub.4                                                                          K                           "  "       3-CONH.sub.2                                                                          C.sub.2 H.sub.4 NHCOCH.sub.3                                                            C.sub.2 H.sub.5                                                                            "           K                           "  C.sub.6 H.sub.4p-Br                                                                    3-CH.sub.2 CN                                                                         C.sub.2 H.sub.4 CONH.sub.2                                                              CH.sub.3    "           K                           "  SO.sub.2 CH.sub.3                                                                      3-CH.sub.2 CN                                                                         C.sub.2 H.sub.4 NHCOCH.sub.3                                                            C.sub.2 H.sub.5                                                                            "           K                           "  SO.sub.2 NHCH.sub.3                                                                    3-C.sub.6 H.sub.5                                                                     "        C.sub.6 H.sub.5                                                                            "           K                           __________________________________________________________________________

                                      TABLE 7                                      __________________________________________________________________________      ##STR22##                                                                     Posi-                                                                          tion                                                                              R       R.sup.1                                                                               Q  Q' R.sup.12                                                                              R.sup.13                                                                              X'Z    M                                 __________________________________________________________________________     3  H       H      CO CO C.sub.6 H.sub.5                                                                       C.sub.6 H.sub.5                                                                       NHC.sub.2 H.sub.4                                                                     Na                                "  H       4-CH.sub.3                                                                            CO CO CH.sub.3                                                                              CH.sub.2 OH                                                                           "      Na                                "  H       4-C.sub.6 H.sub.5                                                                     CN CO --     NHCO.sub.2 C.sub.2 H.sub.5                                                            OC.sub.2 H.sub.4                                                                      Na                                "  CH.sub.3                                                                               4-CH.sub.3                                                                            CN CO --     CH.sub.3                                                                              NHC.sub.2 H.sub.4                                                                     Na                                "  C.sub.6 H.sub.4p-Br                                                                    H      CO SO.sub.2                                                                          NH.sub.2                                                                              OC.sub.6 H.sub.5                                                                      "      "                                 "  "       4-CH.sub.2 CN                                                                         CO SO.sub.2                                                                          CH.sub.3                                                                              OCH.sub.3                                                                             "      "                                 "  SO.sub.2 C.sub.6 H.sub.5                                                               4-C.sub.6 H.sub.5                                                                     CN SO.sub.2                                                                          --     C.sub.6 H.sub.5                                                                       "      "                                 4  H       3-CONH.sub.2                                                                          CO CO CH.sub.2 C(CH.sub.3).sub.2 CH.sub.2                                                          "      K                                 "  H       H      CO CO 1,2-C.sub.6 H.sub.4                                                                          "      K                                 "  H       3-CONH.sub.2                                                                          CO CO C.sub.2 H.sub.5                                                                       OC.sub.2 H.sub.5                                                                      "      K                                 "  H       H      CO CO CF.sub.3                                                                              H      "      K                                 "  CH.sub.3                                                                               H      CO CO OCH.sub.3                                                                             H      "      K                                 "  "       3-CH.sub.3                                                                            CO CO CH.sub.2 Cl                                                                           H      "      K                                 "  SCN     3-C.sub.6 H.sub.5                                                                     CO CO "      CH.sub.3                                                                              "      K                                 "  C.sub.2 H.sub.4 OCH.sub.3                                                              3-CH.sub.3                                                                            CO CO NHC.sub.2 H.sub.5                                                                     NH.sub.2                                                                              N(CH.sub.3)C.sub.2 H.sub.4                                                            K                                 "  C.sub.2 H.sub.4 CN                                                                     3-COCH.sub.3                                                                          CO CO NHC.sub.2 H.sub. 5                                                                    NH.sub.2                                                                              N(C.sub.6 H.sub.5)C.sub.2 H.sub.4                                                     K                                 "  C.sub.6 H.sub.5                                                                        3-C.sub.6 H.sub.5                                                                     CO CO OC.sub.2 H.sub.5                                                                      C.sub.2 H.sub.5                                                                       NHC.sub.2 H.sub.4                                                                     K                                 "  "       H      CO CO OCH.sub.2C.sub.6 H.sub.5                                                              "      NHC.sub.2 H.sub.4                                                                     K                                 "  "       3-CONHCH.sub.3                                                                        CO CO OC.sub.6 H.sub.11                                                                     OCH.sub.3                                                                             NHC.sub.2 H.sub.4                                                                     K                                 "  "       3-CH.sub.3                                                                            CO CO C.sub.6 H.sub.5                                                                       OCH.sub.3                                                                             NHC.sub.2 H.sub.4                                                                     K                                 "  "       3-C.sub.2 H.sub.4 Cl                                                                  CO CO NHCOC.sub.2 H.sub.5                                                                   NHCO.sub.2 C.sub.2 H.sub.5                                                            NHC.sub.2 H.sub.4                                                                     K                                 "  "       3-Br   CO CO NHSO.sub.2 C.sub.2 H.sub.5                                                            NHCO.sub.2 C.sub.2 H.sub.5                                                            NHC.sub.2 H.sub.4                                                                     K                                 "  C.sub.6 H.sub.4p-OCH.sub.3                                                             "      CO CO NHCOC.sub.6 H.sub.5                                                                   NHCO.sub.2 C.sub.2 H.sub.5                                                            NHC.sub.2 H.sub.4                                                                     K                                 "  "       3-CONH.sub.2                                                                          CO CO OC.sub.2 H.sub.5                                                                      NHCO.sub.2 C.sub.2 H.sub.5                                                            NHC.sub.2 H.sub.4                                                                     K                                 __________________________________________________________________________

                                      TABLE 8                                      __________________________________________________________________________      ##STR23##                                                                     Posi-             OH                                                           tion                                                                              R       R.sup.1                                                                               Position                                                                            R.sup.2   X'Z         M                                 __________________________________________________________________________     3  H       H      2    5-CH.sub.3                                                                               NHC.sub.2 H.sub.4                                                                          Na                                "  H       4-CH.sub.3                                                                            2    5-CH.sub.3                                                                               OC.sub.2 H.sub.4                                                                           Na                                "  H       4-C.sub.6 H.sub.5                                                                     2    5-OCH.sub.3                                                                              NHC.sub.2 H.sub.4                                                                          K                                 "  CH.sub.3                                                                               4-CH.sub.3                                                                            2    5-Cl      "           Na                                "  C.sub.6 H.sub.4p-Br                                                                    H      2    5-Cl      "           Na                                "  "       4-CH.sub.2 CN                                                                         4    3-OCH.sub.3                                                                              "           K                                 "  SO.sub.2 C.sub.6 H.sub.5                                                               4-C.sub.6 H.sub.5                                                                     4    3-OCH.sub.3                                                                              "           K                                 4  H       3-CONH.sub.2                                                                          3,4  H         "           Na                                "  H       H      4    2-NHC.sub.6 H.sub.5                                                                      "           Na                                "  H       3-CONH.sub.2                                                                          2    5-NHCOCH.sub.3                                                                           "           Na                                "  H       H      3,4  H         N(CH.sub.3)C.sub.2 H.sub.4                                                                 K                                 "  CH.sub.3                                                                               H      2                                                                                    ##STR24##                                                                               NHC.sub.2 H.sub.4                                                                          K                                                        C.sub.2 H.sub.4 OSO.sub.3 K                             "  "       3-CH.sub.3                                                                            2    5-C.sub.6 H.sub.11                                                                       NHC.sub.2 H.sub.4                                                                          K                                 "  SCN     3-C.sub.6 H.sub.5                                                                     2    5-OC.sub.6 H.sub.5                                                                       N(C.sub.6 H.sub.5)C.sub.2 H.sub.4                                                          "                                 "  C.sub.2 H.sub.4 OCH.sub.3                                                              3-CH.sub.3                                                                            2    5-SCH.sub.3                                                                              NHC.sub.2 H.sub.4                                                                          K                                 "  C.sub.2 H.sub.4 CN                                                                     3-COCH.sub.3                                                                          2    5-SC.sub.6 H.sub.5                                                                       NHCH.sub.2CH(C.sub.6 H.sub.5)                                                              Na                                "  C.sub.6 H.sub.5                                                                        3-C.sub.6 H.sub.5                                                                     2    5-NHCOOCH.sub.3                                                                          OC.sub.2 H.sub.4                                                                           Na                                "  "       H      2    5-NHSO.sub.2 CH.sub.3                                                                    NHC.sub.2 H.sub.4 OC.sub.2 H.sub.4                                                         Na                                "  "       3-CONHCH.sub.3                                                                        2    5-NHCOCH.sub.3                                                                           NHC.sub.2 H.sub.4                                                                          NH.sub.4                          "  "       3-CH.sub.3                                                                            2    5-NHCOCH.sub.2 Cl                                                                        OC.sub.2 H.sub.4                                                                           K                                 "  "       3-C.sub.2 H.sub.4 Cl                                                                  2    5-NHCOC.sub.2 H.sub.4 OH                                                                 OC.sub.2 H.sub.4                                                                           K                                 "  "       3-Br   2    5-Cl      NHC.sub.3 H.sub.6                                                                          K                                 "  C.sub.6 H.sub.4p-OCH.sub.3                                                             "      2    5-NHCONHC.sub.2 H.sub.5                                                                  OC.sub.2 H.sub.4                                                                           NH.sub.4                          "  "       3-CONH.sub.2                                                                          2    5-NHCON(C.sub.2 H.sub.5).sub.2                                                           NHC.sub.2 H.sub.4                                                                          K                                 "  C.sub.6 H.sub.4p-Br                                                                    3-CH.sub.2 CN                                                                         2    5-CH.sub.3                                                                               "           "                                 "  SO.sub.2 CH.sub.3                                                                      3-CH.sub.2 CN                                                                         2    5-NHCOCH.sub.3                                                                           "           "                                 "  SO.sub.2 NHCH.sub.3                                                                    3-C.sub.6 H.sub.5                                                                     4    H         "           Na                                __________________________________________________________________________

                                      TABLE 9                                      __________________________________________________________________________      ##STR25##                                                                     Posi-             OH                                                           tion                                                                              R       R.sup.1                                                                               Position                                                                            R.sup.2   R.sup.14                                                                               X'Z         M                         __________________________________________________________________________     3  H       H      2    H         6-SO.sub.2 N(CH.sub.3).sub.2                                                           NHC.sub.2 H.sub.4                                                                          Na                        "  H       4-CH.sub.3                                                                            2    H         "       "           "                         "  H       4-C.sub.6 H.sub.5                                                                     2    3-CONH.sub.2                                                                             H       "           Na                        "  CH.sub.3                                                                               4-CH.sub.3                                                                            4    H         H       N(CH.sub.3)C.sub.2 H.sub.4                                                                 "                         "  C.sub.6 H.sub.4p-Br                                                                    H      4    H         H       OC.sub. 2 H.sub.4                                                                          K                         "  "       4-CH.sub.2 CN                                                                         2,6  H         H       OC.sub.2 H.sub.4 OC.sub.2                                                      H.sub.4     K                         "  SO.sub.2 C.sub.6 H.sub.5                                                               4-C.sub.6 H.sub.5                                                                     2    H         H       OC.sub.2 H.sub.4                                                                           K                         4  H       3-CONH.sub.2                                                                          "    H         6-SO.sub.2 NHCH.sub.3                                                                  OC.sub.2 H.sub.4 OC.sub.2                                                      H.sub.4     K                         "  H       H      2    3-CONH.sub.2                                                                             H       NHC.sub.2 H.sub.4                                                                          Na                        "  H       3-CONH.sub.2                                                                          2    3-CONHC.sub.6 H.sub.5                                                                    H       NHCH(C.sub.2 H.sub.5)CH.sub.2                                                              Na                        "  H       H      2    3-CONHC.sub.6 H.sub.4p                                                                   H       OC.sub.2 H.sub.4                                                                           NH.sub.4                                         OC.sub.2 H.sub.4 OH                                     "  CH.sub.3                                                                               H      4    H         H       NHC.sub.2 H.sub.4                                                                          Na                        "  "       3-CH.sub.3                                                                            4    H         H       NHC.sub.2 H.sub.4                                                                          Na                        "  SCN     3-C.sub.6 H.sub.5                                                                     4    H         H       "           "                         "  C.sub.2 H.sub.4 OCH.sub.3                                                              3-CH.sub.3                                                                            2    H         H       NHC.sub.2 H.sub.4                                                                          K                         "  C.sub.2 H.sub.4 CN                                                                     3-COCH.sub.3                                                                          2    "         "       NHCH.sub.2CH(C.sub.                                                                        K H.sub.5)                "  C.sub.6 H.sub.5                                                                        3-C.sub.6 H.sub.5                                                                     2    3-CO.sub.2 CH.sub.3                                                                      "       OC.sub.2 H.sub.4                                                                           Na                        "  "       H      2    "         "       NHC.sub.2 H.sub.4 OC.sub.2                                                     H.sub.4     Na                        "  "       3-CONHCH.sub.3                                                                        2,4  H         H       NHC.sub.2 H.sub.4                                                                          NH.sub.4                  "  "       3-CH.sub.3                                                                            2    3-COCH.sub.2 Cl                                                                          "       OC.sub.2 H.sub.4                                                                           K                         "  "       3-C.sub.2 H.sub.4 Cl                                                                  4    H         "       OC.sub.2 H.sub.4                                                                           K                         "  "       3-Br   4    H         H       NHC.sub.3 H.sub.6                                                                          K                         "  C.sub.6 H.sub.4p-OCH.sub.3                                                             "      4    H         "       OC.sub.2 H.sub.4                                                                           NH.sub.4                  "  "       3-CONH.sub.2                                                                          4    H         "       NHC.sub.2 H.sub.4                                                                          K                         "  C.sub.6 H.sub.4p-Br                                                                    3-CH.sub.2 CN                                                                         4    H         "       "           "                         "  SO.sub.2 CH.sub.3                                                                      3-CH.sub.2 CN                                                                         2    3-CONHC.sub.6 H.sub.5                                                                    "       "           "                         "  SO.sub.2 NHCH.sub.3                                                                    3-C.sub.6 H.sub.5                                                                     2    H         "       N(C.sub.6 H.sub.5 )C.sub.2                                                     H.sub.4     "                         __________________________________________________________________________

                                      TABLE 10                                     __________________________________________________________________________      ##STR26##                                                                     Posi-                                                                          tion                                                                              R       R.sup.1                                                                               R.sup.16      R.sup.17                                                                            R.sup.2                                                                             R.sup.14                                                                            X'Z         M                   __________________________________________________________________________     3  H       H      C.sub.6 H.sub.11                                                                             H    H    H    NHC.sub.2 H.sub.4                                                                          Na                  "  H       4-CH.sub.3                                                                            C.sub.2 H.sub.4 CONH.sub.2                                                                   H    H    "    "           "                   "  H       4-C.sub.6 H.sub.5                                                                     C.sub.2 H.sub.4 SO.sub.2 CHCH.sub.2                                                          H    H    8-OH "           Na                  "  CH.sub.3                                                                               4-CH.sub. 3                                                                           C.sub.2 H.sub.4 NHSO.sub.2 CH.sub.3                                                          H    H    H    N(CH.sub.3)C.sub.2                                                                         ".sub.4             "  C.sub.6 H.sub.4p-Br                                                                    H                                                                                      ##STR27##    H    3-OCH.sub.3                                                                         8-OH OC.sub.2 H.sub.4                                                                           K                   "  "       4-CH.sub.2 CN                                                                         C.sub.2 H.sub.4 OC.sub.2 H.sub.4 OCH.sub.3                                                   H    H    H    OC.sub.2 H.sub.4 OC.sub.2                                                      H.sub.4     K                   "  SO.sub.2 C.sub.6 H.sub.5                                                               4-C.sub.6 H.sub.5                                                                     CH(CH.sub.3)C.sub.2 H.sub.5                                                                  H    H    H    OC.sub.2 H.sub.4                                                                           K                   4  H       3-CONH.sub.2                                                                          CH(CH.sub.3)CH.sub.2 CH(CH.sub.3)CH.sub.3                                                    CH.sub.3                                                                            H    H    OC.sub.2 H.sub.4 OC.sub.2                                                      H.sub.4     K                   "  H       H      C.sub.6 H.sub.5                                                                              H    3-OCH.sub.3                                                                         H    NHC.sub.2 H.sub.4                                                                          Na                  "  H       3-CONH.sub.2                                                                          C.sub.2 H.sub.5                                                                              C.sub.2 H.sub.4 OH                                                                  "    H    NHCH(C.sub.2 H.sub.5)CH.sub                                                    .2          Na                  "  H       H      CH.sub.2 CH(OH)CH.sub.2 OH                                                                   "    H    H    OC.sub.2 H.sub.4                                                                           NH.sub.4            "  CH.sub.3                                                                               H      C.sub.2 H.sub. 4 SO.sub.2 NH.sub.2                                                           H    H    H    NHC.sub.2 H.sub.4                                                                          Na                  "          3-CH.sub.3                                                                            (CH.sub.2).sub.3 NHCOCH.sub.3                                                                H    H    H    NHC.sub.2 H.sub.4                                                                          Na                  "  SCN     3-C.sub.6 H.sub.5                                                                     C.sub.2 H.sub.4 OC.sub.2 H.sub.4 OH                                                          H    H    H    "           "                   "  C.sub.2 H.sub.4 OCH.sub.3                                                              3-CH.sub.3                                                                            C.sub.3 H.sub.6 OCH.sub.3                                                                    H    H    H    NHC.sub.2 H.sub.4                                                                          K                   "  C.sub.2 H.sub.4 CN                                                                     3-COCH.sub.3                                                                          CH.sub.2 C.sub.6 H.sub.5                                                                     CH.sub.2 C.sub.6 H.sub.5                                                            "    "    NHCH.sub.2CH(C.sub.6                                                           H.sub.5)    K                   "  C.sub.6 H.sub.5                                                                        3-C.sub.6 H.sub.5                                                                     C.sub.6 H.sub.11                                                                             H    H    "    OC.sub.2 H.sub.4                                                                           Na                  "  "       H      C.sub.2 H.sub.4 CONH.sub.2                                                                   H    "    "    NHC.sub.2 H.sub.4 OC.sub.2                                                     H.sub.4     Na                  "  "       3-CONHCH.sub.3                                                                        C.sub.2 H.sub.4 SO.sub.2 CHCH.sub.2                                                          H    H    8-OCH.sub.3                                                                         NHC.sub.2 H.sub.4                                                                          NH.sub.4            "  "       3-CH.sub.3                                                                             ##STR28##    H    3-OC.sub.2 H.sub.5                                                                  8-OC.sub.2 H.sub.5                                                                  OC.sub.2 H.sub.4                                                                           K                   "  "       3-C.sub.2 H.sub.4 Cl                                                                   ##STR29##    H    H    "    OC.sub.2 H.sub.4                                                                           K                   "  "       3-Br   C.sub.2 H.sub.4 OC.sub.2 H.sub.4 OCH.sub.3                                                   H    H    H    NHC.sub.3 H.sub.6                                                                          K                   "  C.sub.6 H.sub.4p-OCH.sub.3                                                             "      CH(CH.sub.3)C.sub.2 H.sub.5                                                                  H    H    "    OC.sub.2 H.sub.4                                                                           NH.sub.4            "  "       3-CONH.sub.2                                                                          CH(CH.sub.3)CH.sub.2 CH(CH.sub.3)CH.sub.3                                                    H    H    "    NHC.sub.2 H.sub.4                                                                          K                   "  C.sub.6 H.sub.4p-Br                                                                    3-CH.sub.2 CN                                                                         C.sub.6 H.sub.5                                                                              H    3-C.sub.2 H.sub.5                                                                   "    "           "                   "  SO.sub.2 CH.sub.3                                                                      3-CH.sub.2 CN                                                                         C.sub.2 H.sub.5                                                                              "    H    "    "           "                   "  SO.sub.2 NHCH.sub.3                                                                    3-C.sub.6 H.sub.5                                                                     CH.sub.2 CH(OH)CH.sub.2 OH                                                                   "    H    "    N(C.sub.6 H.sub.5)C.sub. 2                                                     H.sub.4     "                   __________________________________________________________________________

The invention has been described in detail with particular reference to certain preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention. 

We claim:
 1. A dye of the formula: ##STR30## wherein R¹ is selected from hydrogen, alkyl, aryl, alkylthio, carbamoyl, alkylcarbamoyl, alkanoyl, cyanoalkyl, and halogen; R is selected from hydrogen, alkyl, aryl, alkanoyl, alkylsulfonyl, arylsulfonyl, alkyl sulfamoyl, arylsulfamoyl, alkyl substituted with alkoxy, cyano, or halogen, and aryl substituted with alkoxy, halogen or cyano; and C is selected from ##STR31## wherein R² and R¹⁴ each represents up to three groups selected from hydrogen, fluorine, chlorine, bromine, alkyl, cycloalkyl, alkoxy, phenoxy, alkylthio, arylthio, and radicals having the formula --NH--X--R³ in which X is --CO--, --COO--, or --SO₂ -- and R³ is selected from alkyl and alkyl substituted with halogen, hydroxy, phenoxy, aryl, cyano, cycloalkyl, alkylsulfonyl, alkylthio, alkanoyloxy, and alkoxy, and when X is --CO--, R³ also is selected from hydrogen, amino, alkylamino, dialkylamino, arylamino, aryl, and furyl;R⁴ and R⁵ are each selected from hydrogen, alkyl, aryl, cycloalkyl, and alkyl substituted with halogen, CN, OH, alkoxy, aryloxy, alkoxyalkoxy, alkanoyl, alkanolyloxy, carbamoyl, alkylcarbamoyl, sulfamoyl, alkylsulfamoyl, alkoxyalkanoyloxy, and cycloalkyl, and R⁴ and R⁵ together represent a single, combined group --CH₂ CH₂ CH₂ CH₂ CH₂ --, --CH₂ CH₂ OCH₂ CH₂ --, --CH₂ CH₂ --S--CH₂ CH₂ --, or --CH₂ CH₂ --SO₂ --CH₂ CH₂ --; R⁸ represents one or two groups each selected from hydrogen, alkyl and alkyl substituted with --CN, alkoxy, alkoxycarbonyl, alkoxycarbonyloxy, phenyl, cyclohexoxy, --OH, --Cl and Br; R⁹, R¹⁰ and R¹¹ are each selected from hydrogen, alkyl, phenyl, or phenyl substituted with 1-3 groups selected from Cl, Br, alkyl or alkoxy, alkylthio, benzylthio, cyclohexylthio and phenylthio; Q and Q' are each selected from --CO--, --SO₂ --, or --CN; R¹² and R¹³ are each selected from alkyl, hydroxyalkyl, alkoxy, alkoxycarbonylamino, trifluoromethyl, phenyl or phenyl substituted with 1-3 groups selected from Cl, Br, alkyl or alkoxy, alkoxycarbonylalkyl, cyanoalkyl, amino, haloalkyl, alkylamino, alkylthio, benzylthio, cyclohexylthio and phenylthio; and R¹² and R¹³ together comprise --CH₂ C(CH₃)₂ CH₂ --, or 1,2-C₆ H₄ -- connecting Q and Q'; R¹⁶ and R¹⁷ are selected from hydrogen, cycloalkyl, aryl, alkyl, and alkyl substituted with alkoxy, hydroxy, alkoxyalkoxy, hydroxyalkoxy, carbamoyl, sulfamoyl, alkanoylamino, or alkenylsulfonyl, and aryl substituted with hydroxyalkyl; e is 1 or 2; t and t' are each 1 or zero; X' is O, NH, N(alkyl)--, or N(aryl)--; Z is selected from straight- or branched-chain alkylene, and such alkylene substituted with phenyl, halogen, OSO₃ M, alkoxy or aryloxy groups, --CH₂ (CH₂)_(m) V--CH₂ (CH₂)_(p) --, where m is 1, 2 or 3, p is 0, 1, 2 or 3, and V is O, S, SO₂, --SO₂ NH--, --SO₂ N(alkyl)--, --SO₂ N(aryl), --N(SO₂ aryl)--, --NH, --NHCO--, --NHCONH, --N(SO₂ alkyl), or --CON(alkyl); M is H, Na, K or NH₄ ; n is 1 or 2; and wherein each of the above alkyl and alkoxy groups contain from 0 to three of the following: hydroxy; halogen; cyano; succinimido; glutarimido; phthalimido; 2-pyrrolidono; cyclohexyl; phenyl or phenyl substituted with alkyl, alkoxy, halogen, alkanoylamino, cyano or alkoxycarbonyl; alkanoylamino; sulfamoyl; alkyl-sulfamoyl; vinylsulfonyl; acrylamido; phthalimidinyl; benzoylsulfonicimidyl; alkylsulfonamido; phenylsulfonamido; alkoxycarbonylamino; alkylcarbamoyloxy; alkoxycarbonyl; alkoxybonyloxy; ##STR32## wherein Y is --NH--, --NH-alkyl--, --O--, --S--, or --CH₂ O--; --S--R⁶, wherein R⁶ is alkyl, phenyl, phenyl substituted with halogen, alkyl, alkoxy, alkanoylamino, cyano, or alkoxycarbonyl, pyridyl, pyrimidinyl, benzoxazolyl, benzimidazolyl, benzothiazolyl, or ##STR33## --SO₂ R³ ; --COOR³ ; --OXR³ ; --NH--X--R³ ; --X--R³ ; --SO₂ NR⁷ R⁷ ; wherein R³ and X are as defined above and each R⁷ is selected from H and R³ ; alkoxy; alkoxy substituted with hydroxy, cyano, alkanoyloxy, or alkoxy; phenoxy; or phenoxy substituted with one or more of alkyl, alkoxy or halogen.
 2. The dye according to claim 1 of the formula ##STR34##
 3. The dye according to claim 1 of the formula ##STR35##
 4. The dye according to claim 1 of the formula ##STR36## 